Liquid stabilizer mixture

ABSTRACT

A mixture comprising
         (a) one or more liquid UV absorbers, with the proviso that Tinuvin 384-2 as a liquid UV absorber is excluded,   (b) one or more branched polymers comprising stabilizing groups,   (c) optionally one or more further additions.
 
Use of such a mixture for stabilizing inanimate organic materials against the effect of light, oxygen and/or heat. Inanimate organic materials comprising at least one such mixture, and also articles produced from such inanimate organic materials. Methods of stabilizing inanimate organic materials against the effect of light, oxygen and/or heat by adding to said inanimate organic materials at least one such mixture in an effective amount.

The invention relates to mixtures which comprise

-   -   (a) one or more liquid UV absorbers, with the proviso that        Tinuvin 384-2 as a liquid UV absorber is excluded,    -   (b) one or more branched polymers comprising stabilizing groups,    -   (c) optionally one or more further additions.

The present invention additionally discloses methods of stabilizinginanimate organic materials, more particularly plastics, against theeffect of light, oxygen and/or heat, using this mixture. The inventionfurther relates to articles produced from inanimate organic materialsthus stabilized.

Further embodiments of the present invention are evident from theclaims, the description, and the examples. It is understood that thefeatures of the inventive subject matter that are specified above, andthose still to be elucidated below, can be used not only in the specificcombination in which they are given in each case, but also in othercombinations as well, without departing the scope of the invention.Preference, and very great preference, respectively, is also given moreparticularly to those embodiments of the present invention in which allof the features of the inventive subject matter have the preferred and,respectively, very preferred definitions.

Inanimate organic materials, more particularly plastics, are known to bedestroyed, often rapidly, by the action especially of light, oxygenand/or heat. This destruction is typically manifested in yellowing,discoloration, cracking or embrittlement of the material. The aim ofstabilizers, such as light stabilizers, for example, is therefore toobtain satisfactory protection against the destruction of inanimateorganic material by light, oxygen and/or heat.

Derivatives of 2,2,6,6-tetraalkylpiperidine have been employedcommercially for approximately three decades, under the name HALS(Hindered Amine Light Stabilizers), as light stabilizers and asstabilizers, more particularly for plastics and coating materials.

It is also known to the skilled worker that mixtures of two or morestabilizers, such as antioxidants, HALS compounds and/or UV absorbers,for example, can be employed for the purpose of stabilizing polymers.

EP 1 363 883 B1 discloses stabilizers which comprise HALS compounds.They are used for stabilizing polymers. That specification alsodescribes compositions which among other components may also comprise UVabsorbers.

EP 1 060 225 B1 describes a process for preparing liquid polyfunctionaladditives. These polyfunctional additives are used for stabilizingorganic material, polymers for example. Besides the polyfunctionaladditives the stabilized materials may additionally comprise furtheradditives, such as UV absorbers, for example.

WO 02/092668 A1 describes additives which comprise known polymeradditives in the form of groups attached chemically to hyperbranched ordendritic polymers or copolymers. These polymer additives may be UVabsorbers or else HALS compounds, for example. That specification alsodiscloses compositions comprising these stabilizers. Furthermore, thesecompositions may also comprise other conventional additives, such as UVabsorbers or light stabilizers, for example.

WO 2004/094505 A1 discloses stabilizers composed of highly branchedpolymers having functional groups, as a highly branched anchor group,and one or more stabilizing groups, which protect plastics againstdamage due to heat, UV radiation, oxidation, hydrolysis or mechanicalexposure during processing, the stabilizing groups being coupled to theanchor group via functional groups which are able to react with thefunctional groups of the highly branched polymers.

WO 2005/070987 A1 discloses stabilizers composed of one or morepolyisocyanates having on average 2 to 10 isocyanate groups per moleculeand, per mole of isocyanate groups, 0.1 to 1.0 mol of one or morestabilizing groups, which protect plastics against damage due to heat,UV radiation, oxidation, hydrolysis or mechanical exposure duringprocessing, the stabilizing groups being coupled to the polyisocyanatesvia functional groups which are able to react with the isocyanategroups. The stabilizing groups are selected from phenols, stericallyhindered amines (HALS compounds), benzotriazoles, benzophenones,aromatic amines, and phosphites.

Our unpublished international application PCT/EP2007/057427 describesbranched additives which can be used as stabilizers in polymers. Thebranched additives of PCT/EP2007/057427 may comprise HALS compounds andare used for stabilizing thermoplastics and thermosets against, forexample, oxidative, thermal or radiation-induced degradation.

The stabilized thermoplastic molding compounds disclosed in WO2006/048206 A1 may comprise branched stabilizers having HALS groups.

Although these compounds and mixtures are already established incommercial practice, there nevertheless remains room for improvements,more particularly in respect of the handling of the stabilizers and themiscibility of the stabilizers with the compounds that are to bestabilized. Oftentimes it is the case that stabilizers or their mixturesare solid substances, which frequently, in the form of powders, are noteasy to meter. In certain cases, furthermore, it is difficult toincorporate solid stabilizers into the materials to be stabilized whileachieving a homogeneous distribution of the stabilizers. In these casesit is frequently necessary to disperse or dissolve the stabilizers in asolvent. That approach, however, entails additional worksteps. Moreover,dissolved or dispersed stabilizers have lower concentrations ofeffective compound and their transportation is therefore unfavorable.Frequently moreover, liquid components are already used in thepreparation or processing of the material to be stabilized (examplesbeing polyols in the preparation of polyurethanes, or plasticizers inthe processing of plastics). In this case, of course, the admixing of aliquid additive is particularly beneficial.

It was an object of the present invention, therefore, to providemixtures which are easy to handle and easy to incorporate into thematerials to be stabilized. A further object of the invention was toprovide liquid stabilizer mixtures which can be incorporated in liquidform into the materials to be stabilized, do not have any tendency tomigrate from the stabilized materials, and at the same time exhibit alow volatility. A further sub-object of the present invention was toprovide mixtures, more particularly liquid mixtures, which have a highstabilizer concentration and can also be transported economically. Afurther object of the invention was to provide mixtures whichefficiently stabilize materials against the effect of light, oxygenand/or heat.

Accordingly, the mixtures described at the outset have been found.

For the purposes of this invention, expressions of the form C_(a)-C_(b)identify chemical compounds or substituents having a particular numberof carbon atoms. The number of carbon atoms can be selected from theentire range from a to b, including a and b; a is at least 1 and b isalways greater than a. The chemical compounds or substituents arefurther particularized by expressions of the form C_(a)-C_(b) V. V hereis a chemical class of compound or substituent, and represents alkylcompounds or alkyl substituents, for example.

Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine,chlorine or bromine, more preferably fluorine or chlorine.

Heteroatoms are preferably oxygen, nitrogen, sulfur or phosphorus.

The various collective terms indicated have the following particulardefinition unless otherwise indicated:

C₁-C₃₀ alkyl: straight-chain or branched hydrocarbon radicals having upto 30 carbon atoms, examples being C₁-C₁₈ alkyl, C₁-C₁₀ alkyl or C₁₁-C₂₀alkyl, preferably C₁-C₁₀ alkyl, e.g., C₁-C₆ alkyl, C₁-C₄ alkyl, C₁-C₃alkyl, such as methyl, ethyl, n-propyl, isopropyl, or C₄-C₆ alkyl,n-butyl, sec-butyl, 1,1-dimethylethyl, pentyl, 2-methylbutyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl,1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl,1,1,2-trimethyl-propyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,1-ethyl-2-methylpropyl, or C₇-C₁₀ alkyl, such as heptyl, octyl,2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl ordecyl (e.g., 2-propylheptyl), and also their isomers.

C₂-C₂₂ alkenyl: unsaturated, straight-chain or branched hydrocarbonradicals having 2 to 22 carbon atoms and at least one double bond,preferably one double bond, in any desired position, examples beingC₂-C₁₀ alkenyl or C₁₁-C₂₂ alkenyl, preferably C₂-C₁₀ alkenyl such asC₂-C₄ alkenyl, such as ethenyl, 1-propenyl, 2-propenyl,1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, or C₅-C₆alkenyl, such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl or 1-ethyl-2-methyl-2-propenyl, and alsoC₇-C₁₀ alkenyl, such as the isomers of heptenyl, octenyl, nonenyl ordecenyl.

C₃-C₁₅ cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 upto 15 carbon ring members, preferably C₃-C₈ cycloalkyl such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl orcyclooctyl, and also a saturated or unsaturated polycyclic system suchas norbornyl or norbenzyl, for example. Particular preference is givento C₅-C₆ cycloalkyl.

Aryl: mono- to tricyclic aromatic ring system comprising 6 to 14 carbonring members, e.g., phenyl, hydroxyphenyl, naphthyl or anthracenyl,preferably a mono- to dicyclic, more preferably a monocyclic aromaticring system.

Heterocycles: five- to twelve-membered, preferably five- tonine-membered, more preferably five- to six-membered ring systemscontaining oxygen, nitrogen and/or sulfur atoms, if appropriatecontaining two or more rings, such as furyl, thiophenyl, pyrryl,pyridyl, imidazolyl, indolyl, benzoxazolyl, dioxolyl, dioxyl,benzimidazolyl, benzo-thiazolyl, dimethylpyridyl, methylquinolyl,dimethylpyrryl, methoxyfuryl, dimethoxy-pyridyl, difluoropyridyl,methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.

C₁-C₂₀ alkoxy is a straight-chain or branched alkyl group having 1 to 20carbon atoms (as specified above) which are attached via an oxygen atom(—O—), examples being C₁-C₁₀ alkoxy such as n-hexoxy, isohexoxy,n-octoxy, 2-ethylhexoxy, and isooctoxy, and additionally also methoxy,ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,tert-butoxy, n-pentoxy, n-nonoxy, n-decoxy, or C₁₁-C₂₀ alkoxy such asn-undecoxy and n-dodecoxy, preferably C₁-C₁₀ alkyloxy, more preferablyC₁-C₈ alkoxy, such as methoxy, ethoxy, propoxy or octoxy, for example.

C₁-C₂₂ alkylene: straight-chain or branched hydrocarbon radicals having1 to 22 carbon atoms, examples being C₂-C₁₀ alkylene or C₁₁-C₂₂alkylene, preferably C₂-C₁₀ alkylene, more particularly methylene,dimethylene, trimethylene, tetramethylene, penta-methylene orhexamethylene.

Substances that are “liquid” are substances, in the context of thepresent application, which at temperatures of 5 to 40° C. and a pressureof 500 to 1500 mbar present as good as no resistance to dimensionalchange but present extremely great resistance to a volume change. Afurther feature of the liquid substances is that they have a dynamicviscosity in the range from 1 to 150 000 mPa·s, preferably to 10 000mPa·s, determined at 23° C. and 1 bar, in accordance for example withDIN 53019.

By “dendrimeric” is meant, in the context of the present invention, thatthe degree of branching (DB) is 99.9%-100%. On the definition of thedegree of branching see H. Frey et al., Acta Polym. 1997, 48, 30.

“Hyperbranched polymers” are molecularly and structurally nonuniform.They differ from linear polymers in that they comprise side groups whichare composed of the same monomers as the polymer backbone. They furtherdiffer, for example, in their molecular nonuniformity from dendrimers,and are considerably easier to prepare. By “hyperbranched” is alsomeant, in the context of the present invention, that the degree ofbranching is 10% to 99.9%, preferably 20% to 99%, more preferably 20% to95%.

The degree of branching (DB) is defined as

${{DB} = {\frac{T + Z}{T + Z + L} \times 100\%}},$

where T is the average number of terminally bonded monomer units, Z isthe average number of monomer units which form branches, and L is theaverage number of linearly bonded monomer units in the macromolecules ofthe compounds in question.

“Branched polyisocyanates” for the purposes of this invention areoligomeric and polymeric isocyanates which comprise groups formed by thereaction of polyvalent isocyanates. The groups in question are, forexample, urethane, allophanate, urea, biuret, uretdione, amide,isocyanurate, carbodiimide, uretonimine, oxadiazinetrione oriminooxadiazinedione groups, which in some cases lead to branching. Thebranched polyisocyanates can therefore be characterized as oligomeric orpolymeric compounds (dimers, trimers, tetramers or higher multimers) ofthe polyvalent isocyanates.

“Hyperbranched polycarbonates” for the purposes of this invention arenoncrosslinked macromolecules with hydroxyl and carbonate or carbamoylchloride groups which are both structurally and molecularly nonuniform.In one version of the present invention they may have a composition,starting from a central molecule, analogous with that of dendrimers, butwith a nonuniform branch chain length. In another version of the presentinvention they may be of linear composition, with functional sidegroups, or else may, as a combination of the two extremes, have linearand branched moieties. On the definition of dendrimeric andhyperbranched polymers see also P. J. Flory, J. Am. Chem. Soc. 1952, 74,2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.

“Branched polymers” may for example be branched polyisocyanates orhyperbranched polycarbonates.

“Stabilizing additives” are known. Their function is to protectcompounds against the adverse influence of detrimental environmentaleffects, caused for example by light, oxygen and/or heat. Examples ofsuch stabilizing additives include antioxidants, hydrolysis inhibitors,quenchers, flame retardants or light stabilizers.

“Stabilizing groups” are frequently based on stabilizing additives.These are the part or parts of the stabilizing additive whose effect oninteraction with light, heat, oxygen, peroxides, free radicals and/orother damaging molecules or conditions is to prevent or at least reducethe damage. The stabilizing groups are attached covalently to thebranched polymers. Preferably the stabilizing groups are attachedcovalently to the chain ends of the branched polymers. In principle abranched polymer may comprise one or more stabilizing groups, includingdifferent stabilizing groups. The number and the proportion of thestabilizing groups to one another are variable and are limited only bythe number of attachment points in the branched polymer (covalent bonds)to the stabilizing groups. In this context, however, it is not necessaryfor every attachment point to have been reacted with a stabilizinggroup. Where a branched polymer comprising stabilizing groups (b) is toact, for example, as an antioxidant, that polymer may comprise thosestabilizing groups which retard or arrest the oxidative degradation of aplastic.

In the mixtures of the invention, component (a) comprises one or moredifferent liquid UV absorbers.

Liquid UV absorbers are frequently commercial products. They are sold,for example, under the trade name Uvinul® by BASF Aktiengesellschaft,Ludwigshafen. The Uvinul® light stabilizers comprise compounds of thefollowing classes: benzophenones, benzotriazoles, cyanoacrylates,cinnamic esters, para-aminobenzoates, and naphthalimides. Furthermore,other known chromophores are used, examples being hydroxyphenyltriazinesor oxalanilides. Compounds of this kind are used, for example, alone orin mixtures with other light stabilizers in cosmetic applications, sunprotection products for example, or for stabilizing organic polymers.Preferred liquid UV absorbers are cyanoacrylates, cinnamic esters,benzotriazoles or triazines. Liquid UV absorbers used with particularpreference are 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate or2-ethylhexyl 4-methoxycinnamate. A liquid UV absorber used with veryparticular preference is 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Afurther liquid UV absorber used with very particular preference is2-ethylhexyl 4-methoxycinnamate.

Further examples of liquid UV absorbers are as follows: 2-ethylhexylN,N-dimethyl-4-aminobenzoate, 3,3,5-trimethylcyclohexyl salicylate,2-ethylhexyl salicylate, isoamyl 4-methoxycinnamate,2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenylpropanoicacid C₇₋₉ alkyl esters,β-[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-tert-butylphenyl]propanoic acidpoly(ethylene glycol) 300 ester,bis{(β-[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-tert-butylphenyl]propanoicacid} poly(ethylene glycol) 300 ester.

Further suitable liquid UV absorbers are evident from the text ofCosmetic Legislation, Vol. 1, Cosmetic Products, European Commission1999, pp. 64-66, hereby expressly incorporated by reference.

Suitable liquid UV absorbers are also described in lines 14 to 30([0030]) on page 6 of EP 1 191 041 A2. The skilled worker knows which ofthese UV absorbers are liquid. This literature reference is herebyincorporated to become part of the disclosure content of the presentinvention.

The liquid UV absorbers do not comprise Tinuvin 384-2 (95%benzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, C7-9-branchedand linear alkyl esters; 5% 1-methoxy-2-propyl acetate), a UV absorberfrom Ciba Speciality Chemicals Inc.

Furthermore, in the mixtures of the invention, component (b) is composedof one or more different branched polymers comprising stabilizinggroups.

In one preferred embodiment of the mixture of the invention the branchedpolymers comprising stabilizing groups (b), or mixtures thereof, areliquid.

Branched polymers comprising stabilizing groups (b) are disclosed, forexample, as “branched polymeric stabilizers” in WO 2004/094505 A1 (p. 4,I. 12-I. 26). The stabilizers disclosed there are hereby expresslyincorporated by reference.

The structure of the branched polymers comprising stabilizing groups (b)is preferably hyperbranched.

Branched polymers comprising stabilizing groups (b) can be prepared, forexample, by the general processes described in WO 2004/094505 A1 (p. 8,I. 71-p. 13, I. 33). The preparation processes disclosed therein areexpressly incorporated by reference.

With regard to the branched polymers comprising stabilizing groups (b)and their preparation, including more particularly the stabilizinggroups described therein (active substance groups, p. 14, I. 1-p. 22, I.4), the full content of WO 2004/094505 A1 is incorporated by reference.Stabilizing compounds on which the stabilizing groups are based areavailable commercially or are obtainable from commercially availablecompounds by means of simple reactions known to the skilled worker.

The mixtures of the invention preferably feature branched polymerscomprising stabilizing groups, as component (b), having a number-averagemolecular weight, Mn, of 100 to 20 000 g/mol, preferably 100-15 000g/mol, more preferably 100-10 000 g/mol, and very preferably 200-5000g/mol.

Preferably the mixture of the invention comprises as component (b)branched polymers comprising HALS compounds as stabilizing groups.

In one preferred embodiment of the mixtures of the invention thebranched polymers comprising stabilizing groups (b) comprise carbonategroups. In this case the polymers are preferably hyperbranched.

The preparation of the hyperbranched polymers comprising carbonategroups and stabilizing groups (b) can take place by the methodsindicated in our international application PCT/EP2007/057427.

In accordance with the specification indicated above, hyperbranchedpolycarbonates (i.e., hyperbranched polymers comprising carbonategroups) with stabilizing groups can be obtained by reacting

-   -   (A) at least one compound having at least three alcoholic        hydroxyl groups, also referred to below as compound (A) or, in        accordance with the number of alcoholic hydroxyl groups,        triol (A) or tetrol (A) or pentol (A), for example, with    -   (B) at least one reagent of the formula I, also referred to        below as reagent (B),

-   -   (C) and at least one reagent of the general formula        X³-(A¹)_(m)-X⁴, also referred to below as reagent (C),        the variables being defined as follows:

-   X¹ and X² are alike or different and are selected from halogen,    bromine for example and chlorine more particularly, C₁-C₂₀ alkoxy,    preferably C₁-C₆ alkoxy groups such as methoxy, ethoxy, n-propoxy,    isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy,    isopentoxy, n-hexoxy and isohexoxy, more preferably methoxy, ethoxy,    n-butoxy, and tert-butoxy; aryloxy, more particularly phenoxy,    1-naphthoxy, 2-naphthoxy or C₁-C₄ alkyl-substituted C₆-C₁₀ aryloxy,    more particularly o-tolyloxy or p-tolyloxy, and O—C(═O)-halogen,    more particularly O—C(═O)—Cl; or X¹ and X² together are a group of    the formula O-Q-O, where Q describes an unsubstituted or substituted    α,ω-alkylene group, more particularly ethylene.

Particularly preferred reagents (B) are phosgene, ethyl chloroformate,diphosgene and triphosgene, and also dialkyl carbonates or diarylcarbonates, examples being dimethyl carbonate, diethyl carbonate,dibutyl carbonate (di-n-butyl carbonate, di-tert-butyl carbonate),di-tert-butyl dicarbonate, di-tert-butyl tricarbonate, diphenylcarbonate, ditolyl carbonate, diethylene carbonate, ethylene carbonate,and propylene carbonate. Very particular preference is given to dimethylcarbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, andpropylene carbonate.

Compound (A) is selected from compounds having at least three alcoholichydroxyl groups, examples being triols (A), tetrols (A) or pentols (A).

Examples of suitable triols (A) are aliphatic, aromatic, and benzylictriols, which may be unalkoxylated or alkoxylated one to 100 times perhydroxyl group, preferably alkoxylated with C₂-C₄ alkylene oxide, suchas ethylene oxide, propylene oxide or 1,2-butylene oxide or mixtures ofethylene oxide and propylene oxide and/or butylene oxide, for example,and more particularly alkoxylated with ethylene oxide or propyleneoxide.

Mention may be made, by way of example, of the following: glycerol,trimethylol-methane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane,1,2,4-butanetriol, tris(hydroxymethyl)amine, tris(hydroxyethyl)amine,tris(hydroxypropyl)amine, tris(hydroxymethyl) isocyanurate,tris(hydroxyethyl) isocyanurate, phloroglucinol, trihydroxytoluene,trihydroxydimethylbenzene, phloroglucides, 1,3,5-benzene-trimethanol,1,1,1-tris(4′-hydroxyphenyl)methane, 1,1,1-tris(4′-hydroxyphenyl)ethane,trifunctional or higher polyfunctional polyetherols based ontrifunctional or higher polyfunctional alcohols and ethylene oxide,propylene oxide or butylene oxide, or polyesterols. Particularpreference here is given to glycerol, 1,1,1-trimethylolpropane, andtheir polyetherols based on ethylene oxide or propylene oxide.

Preferred examples include glycerol and (HO—CH₂)₃C—X⁷, unalkoxylated oralkoxylated one to a hundred times per hydroxyl group with C₂-C₄alkylene oxide, X⁷ being selected from a nitrogen atom and C—R⁶, and R⁶being selected from hydrogen and C₁-C₄ alkyl, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Veryparticular preference is given to glycerol, trimethylolethane,trimethylolpropane, 1,2,4-butanetriol, singly to vigintuply alkoxylatedglycerol, and singly to vigintuply alkoxylated 1,1,1-trimethylolpropane(R⁶═C₂H₅), the alkoxylating agents used being preferably ethylene oxideor propylene oxide or mixtures thereof.

Examples of suitable tetrols (A) are pentaerythritol,bis(trimethylolpropane), and diglycerol, which may be unalkoxylated oralkoxylated one to 100 times per hydroxyl group, preferably alkoxylatedwith C₂-C₄ alkylene oxide, such as ethylene oxide, propylene oxide or1,2-butylene oxide, or mixtures of ethylene oxide and propylene oxideand/or butylene oxide, for example, and more particularly alkoxylatedwith ethylene oxide or propylene oxide.

Examples of suitable pentols (A) also comprise compounds having morethan 5 alcoholic hydroxyl groups per molecule. These includetriglycerol, polyglycerols, hexahydroxybenzene, or sugars, such assorbose, mannose or glucose, for example, more particularly reducedsugars such as sorbitol, for example, which may be unalkoxylated oralkoxylated one to 100 times per hydroxyl group, preferably alkoxylatedwith C₂-C₄ alkylene oxide, such as ethylene oxide, propylene oxide or1,2-butylene oxide or mixtures of ethylene oxide and propylene oxideand/or butylene oxide, for example, and more particularly alkoxylatedwith ethylene oxide or propylene oxide.

The compound (A) is preferably a trihydric or tetrahydric alcohol,specifically glycerol, TMP (1,1,1-tri(hydroxymethyl)propane,trimethylolpropane, CAS# 77-99-6) or pentaerythritol which has beenrandomly etherified with from 1 to 5 mol of ethylene oxide, propyleneoxide, butylene oxide or mixtures thereof per mole of hydroxyl groups ofthe trihydric or tetrahydric alcohol.

Furthermore, reaction is carried out with at least one reagent of thegeneral formula X³-(A¹)_(m)—X⁴, also referred to in the context of thepresent invention as reagent (C), where

-   X³ is a functional group selected from OH, SH, NH₂, NH—C₁-C₄ alkyl,    where C₁-C₄ alkyl has been selected from methyl, ethyl, n-propyl,    isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, such as    NH—CH₃, NH—C₂H₅, NH-n-C₃H₇, NH-iso-C₃H₇, NH-n-C₄H₉, NH-iso-C₄H₉,    NH-sec-C₄H₉, NH-tert-C₄H₉, and also isocyanate, epoxy, examples    being

-    COOH, COOR¹², C(═O)—O—C(═O), C(═O)—Cl, preferably COOH, COOR¹², OH,    and NH₂,-   R¹² is C₁-C₄ alkyl or C₆-C₁₀ aryl-   A¹ is a single bond or a spacer, examples of spacers A¹ being    para-phenylene, meta-phenylene, preferably C₂-C₁₀₀ alkylene,    preferably C₂-C₅₀ alkylene, more preferably up to C₂₀ alkylene,    branched or unbranched, and from one to 6 non-adjacent CH₂ groups    here can, if appropriate, also have been replaced by, respectively,    a sulfur atom, which can also have been oxidized, or by an oxygen    atom. The following spacers may be mentioned by way of example:    —CH₂—, —CH₂—CH₂—, —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—, —(CH₂)₇—,    —(CH₂)₈—, —(CH₂)₉—, —(CH₂)₁₀—, —(CH₂)₁₂—, —(CH₂)₁₄—, —(CH₂)₁₆—,    —(CH₂)₁₈—, —(CH₂)₂₀—, —CH₂—CH(CH₃)—, —CH₂—CH(C₂H₅)—,    —CH₂—CH(CH[CH₃]₂)—, —CH₂—CH(n-C₃H₇)—, —[CH(CH₃)]₂—,    —CH(CH₃)—CH₂—CH₂—CH(CH₃)—, —CH(CH₃)—CH₂—CH(CH₃)—, —CH₂—C(CH₃)₂—CH₂—,    —CH₂—CH(n-C₄H₉)—, —CH₂—CH(iso-C₃H₇)—, —CH₂—CH(tert-C₄H₉)—,    -   —CH₂—O—, —CH₂—O—CH₂—, —(CH₂)₂—O—(CH₂)₂—, —[(CH₂)₂—O]₂—(CH₂)₂—,        —[(CH₂)₂—O]₃—(CH₂)₂—,    -   —CH₂—S—, —CH₂—S—CH₂—, —(CH₂)₂—S—(CH₂)₂—, —[(CH₂)₂—S]₂—(CH₂)₂—,        —[(CH₂)₂—S]₃—(CH₂)₂—, —CH₂—SO—CH₂—, —CH₂—SO₂—CH₂—,    -   very particularly preferred spacers being C₁-C₁₀ alkylene        groups, branched or unbranched, such as —CH₂—, —CH₂—CH₂—,        —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₆—, —(CH₂)₆—, —(CH₂)₇—, —(CH₂)₈—,        —(CH₂)₉—, —(CH₂)₁₀—,-   m is zero or one,-   X⁴ is a group selected from phenol groups, benzophenones, aromatic    amines, and nitrogen-comprising heterocycles, in each case    substituted or unsubstituted; preferably a group selected from    nitrogen-comprising heterocycles, more particularly HALS groups.

X⁴ here assumes the role of the stabilizing group. The reagents (C) areto a very large extent available commercially (e.g.,2,2,6,6-tetramethylpiperidinol or 1,2,2,6,6-penta-methylpiperidinol) orare obtainable from these commercially available compounds by standardmethods of organic synthesis.

Particular examples of phenol groups are sterically hindered phenolgroups, for example phenol groups substituted by one or two isopropylgroups or tert-butyl groups in the ortho position relative to thephenolic OH group. Particularly preferred examples of phenol groups are

A very particularly preferred example of a phenol group is the3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid group.

Particular examples of benzophenone groups are

Examples of aromatic amines are

the variables being defined as follows:

-   R⁶ has been selected from hydrogen,    -   C₁-C₁₂ alkyl, such as methyl, ethyl, n-propyl, isopropyl,        n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,        sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,        isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl,        n-decyl;    -   more preferably C₁-C₄ alkyl, such as methyl, ethyl, n-propyl,        isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl,    -   C₃-C₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,        cycloundecyl, and cyclododecyl; preferably cyclopentyl,        cyclohexyl, and cycloheptyl,    -   C₆-C₁₄ aryl, for example 1-naphthyl, 2-naphthyl, 1-anthracenyl,        2-anthracenyl, 9-anthracenyl and in particular phenyl, benzyl.-   R⁷ has been selected from hydrogen,    -   C₁-C₄ alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl,        isobutyl, sec-butyl, and tert-butyl.

Nitrogen-comprising heterocycles can be aromatic, monounsaturated orsaturated. Nitrogen-comprising heterocycles can comprise one, two orthree nitrogen atoms and can bear one or more substituents; in the caseof aromatic heterocycles, preference is given to one or morehydroxyphenyl substituents.

Examples of aromatic heterocycles are benzotriazoles and triazines, inparticular those of the formulae

which may each bear one or more further substituents, for examplehydroxyl or C₁-C₄ alkyl, in particular tert-butyl, also C(CH₃)₂(C₆H₅) orC(CH₃)₂OH or perfluoro-C₁-C₄ alkyl, in particular CF₃ or n-C₄F₉.Specific examples of nitrogen-comprising aromatic heterocycles havingone or more substituents are

Particular examples of saturated nitrogen-comprising heterocycles arethe substituents which are known as HALS (hindered amine lightstabilizers) and have the formula II a or the formula II b.

the variables being defined as follows:

-   R¹, R², R³, and R⁴ are identical or different and are, independently    of one another, C₁-C₁₂ alkyl such as methyl, ethyl, n-propyl,    isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,    isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl,    n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl,    n-nonyl, n-decyl; more preferably C₁-C₄ alkyl such as methyl, ethyl,    n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, and    in particular each of R¹, R², R³, and R⁴ is identical and is methyl,    -   C₃-C₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,        cycloundecyl, and cyclododecyl; preferably cyclopentyl,        cyclohexyl, and cycloheptyl,        or in each case R¹ and R² and/or R³ and R⁴, together with the        carbon atom to which they are jointly attached, form a 4- to        8-membered ring,-   X⁵ is an oxygen atom, a sulfur atom, an NH group, an N—(C₁-C₄ alkyl)    group, a carbonyl group,    -   preferably an oxygen atom,-   A² is a single bond or a spacer. Examples of spacers A² are    para-phenylene, meta-phenylene, preferably C₁-C₂₀ alkylene, branched    or unbranched, where in each case one to 6 nonadjacent CH₂ groups    can if appropriate be replaced by a sulfur atom, including oxidized    forms, or an oxygen atom. Mention may be made by way of example of    the following spacers:    -   —CH₂—, —CH₂—CH₂—, —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—,        —(CH₂)₇—, —(CH₂)₈—, —(CH₂)₉—, —(CH₂)₁₀—, —(CH₂)₁₂—, —(CH₂)₁₄—,        —(CH₂)₁₆—, —(CH₂)₁₈—, —(CH₂)₂₀—, —CH₂—CH(CH₃)—, —CH₂—CH(C₂H₅)—,        —CH₂—CH(CH[CH₃]₂)—, —CH₂—CH(n-C₃H₇)—, —[CH(CH₃)]₂—,        —CH(CH₃)—CH₂—CH₂—CH(CH₃)—, —CH(CH₃)—CH₂—CH(CH₃)—,        —CH₂—C(CH₃)₂—CH₂—, —CH₂—CH(n-C₄H₉)—, —CH₂—CH(iso-C₃H₇)—,        —CH₂—CH(tert-C₄H₉)—,    -   —CH₂—O—, —CH₂—O—CH₂—, —(CH₂)₂—O—(CH₂)₂—, —[(CH₂)₂—O]₂—(CH₂)₂—,        —[(CH₂)₂—O]₃—(CH₂)₂—, —CH₂—S—, —CH₂—S—CH₂—, —(CH₂)₂—S—(CH₂)₂—,        —[(CH₂)₂—S]₂—(CH₂)₂—, —[(CH₂)₂—S]₃—(CH₂)₂—, —CH₂—SO—CH₂—,        —CH₂—SO₂—CH₂—,    -   preferred spacers A² being C₂-C₁₀ alkylene groups, branched or        unbranched, such as —CH₂—OH₂—, —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—,        —(CH₂)₆—, —(CH₂)₇—, —(CH₂)₈—, —(CH₂)₉—, —(CH₂)₁₀—;    -   preferably A² is a single bond,-   n is zero or one,-   X⁶ is hydrogen, oxygen,    -   O—C₁-C₁₉ alkyl, preferably C₁-C₆ alkoxy groups such as methoxy,        ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,        tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, and isohexoxy,        more preferably methoxy or ethoxy,    -   C₁-C₁₂ alkyl, preferably methyl, ethyl, n-propyl, isopropyl,        n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,        sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,        isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl,        n-decyl; more preferably C₁-C₄ alkyl such as methyl, ethyl,        n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and        tert-butyl,    -   C₂-C₁₈ acyl, for example acetyl, propionyl, butyryl, benzoyl,        stearyl,    -   or aryloxycarbonyl having 7 to 12 C atoms, for example C₆H₅—OCO.

Examples of particularly well-suited HALS compounds (stabilizingadditives) on which the abovementioned stabilizing compounds of theformula IIa or IIb may be based are

-   4-amino-2,2,6,6-tetramethylpiperidine,-   4-amino-1,2,2,6,6-pentamethylpiperidine,-   4-hydroxy-2,2,6,6-tetramethylpiperidine,-   4-hydroxy-1,2,2,6,6-pentamethylpiperidine,-   4-butylamino-2,2,6,6-tetramethylpiperidine,-   4-butylamino-1,2,2,6,6-pentamethylpiperidine,-   4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl,-   4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl,-   4-butylamino-2,2,6,6-tetramethylpiperidine-N-oxyl,-   4-hydroxy-2,2,6,6-tetramethyl-1-octoxypiperidine,-   4-amino-2,2,6,6-tetramethyl-1-octoxypiperidine,-   4-butylamino-2,2,6,6-tetramethyl-1-octoxypiperidine

Very particularly suitable are 4-amino-2,2,6,6-tetramethylpiperidine,4-amino-1,2,2,6,6-pentamethylpiperidine,4-hydroxy-2,2,6,6-tetramethylpiperidine,4-hydroxy-1,2,2,6,6-pentamethylpiperidine,4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl, and4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.

In one preferred embodiment of the mixture of the invention thehyperbranched polycarbonate comprising HALS compounds is obtained byreacting a mixture comprising:

-   -   (A) one or more polyhydric alcohols,    -   (B) one or more carbonates,    -   (C) one or more HALS compounds comprising a functional group        reacting with (A) and/or (B).

More particularly suitable are also HALS compounds of the generalformula (III):

-   -   in which    -   R²¹ is OH, SH, NHR or NH₂,    -   R²² is H, C₁-C₂₂ alkyl, C₁-C₈ alkoxy,    -   R²³, R²⁴, R²⁵, and R²⁶ independently of one another, identically        or differently, are C₁-C₂₂ alkyl, or R²³ and R²⁴ and/or R²⁵ and        R²⁶ together with the carbon atom to which they are attached        form a 4-, 5-, 6-, 7- or 8-membered ring,    -   R²⁷ and R²⁸ independently of one another, identically or        differently, are H or C₁-C₂₂ alkyl    -   and    -   R²¹ reacts with (A) and/or (B).

With very particular preference R²¹═OH, R²²═R²³═R²⁴═R²⁵═R²⁶=methyl, andR²⁷═R²⁸═H.

In one embodiment of the present invention, mixtures of the inventioncomprise hyperbranched polycarbonates with stabilizing groups, acharacteristic feature of which is that these polycarbonates have adynamic viscosity in the range from 100 to 150 000 mPa·s, preferably upto 10 000 mPa·s, determined at 23° C., for example in accordance withDIN 53019.

In one embodiment of the present invention, mixtures of the inventioncomprise hyperbranched polycarbonates with stabilizing groups, acharacteristic feature of which is that these polycarbonates have anumber average molecular weight (M_(n)) of from 100 to 15 000 g/mol,preferably from 200 to 12 000 g/mol and in particular from 400 to 10 000g/mol, which can be determined, for example, by means of GPC, polymethylmethacrylate (PMMA) as standard and dimethylacetamide as eluent.

In one embodiment of the present invention, mixtures of the inventioncomprise hyperbranched polycarbonates with stabilizing groups, acharacteristic feature of which is that these polycarbonates have aglass transition temperature T_(g) in the range from −70 to 10° C.,determined by differential thermoanalysis (differential scanningcalorimetry).

In one embodiment of the present invention, mixtures of the inventioncomprise hyperbranched polycarbonates with stabilizing groups, acharacteristic feature of which is that these polycarbonates have an OHnumber in the range from 0 to 600 mg KOH/g, preferably from 1 to 550 mgKOH/g and in particular from 1 to 500 mg KOH/g (in accordance with DIN53240, part 2).

In one preferred embodiment of the present invention, mixtures of theinvention comprise hyperbranched polycarbonates with stabilizing groups,with the characteristic feature that these polycarbonates have a dynamicviscosity in the range from 100 to 150 000 mPa·s, preferably to 10 000mPa·s, determined at 23° C., in accordance for example with DIN 53019,and that these polycarbonates have a number-average molecular weight(M_(n)) of 100 to 15 000, preferably of 200 to 12 000, and moreparticularly of 400 to 10 000 g/mol, which can be determined, forexample, by means of GPC, polymethyl methacrylate (PMMA) as standard anddimethylacetamide as eluent, and that these polycarbonates have a glasstransition temperature T_(g) in the range from −70° C. to 10° C.,determined by differential thermoanalysis (differential scanningcalorimetry), and that these polycarbonates have an OH number in therange from 0 to 600, preferably 1 to 550, and more particularly from 1to 500 mg KOH/g (in accordance with DIN 53240, part 2).

For the preparation of hyperbranched polycarbonate it is also possibleoptionally to add one or more compounds (D) having two alcoholichydroxyl groups per molecule, for which the abbreviated term compounds(D) is also used. Examples of suitable compounds (D) comprise ethyleneglycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol,dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,2-, 1,3-,and 1,4-butanediol, 1,2-, 1,3-, and 1,5-pentanediol, hexanediol,cyclopentanediol, cyclohexanediol, cyclohexanedimethanol,bis(4-hydroxycyclohexyl)methane, bis(4-hydroxycyclohexyl)ethane,2,2-bis(4-hydroxycyclohexyl)propane,1,1′-bis(4-hydroxyphenyl)-3,3-5-trimethylcyclohexane, resorcinol,hydroquinone, 4,4′-dihydroxyphenyl, bis-(4-bis(hydroxyphenyl) sulfide,bis(4-hydroxyphenyl) sulfone, bis(hydroxymethyl)benzene,bis(hydroxymethyl)toluene, bis(p-hydroxyphenyl)methane,bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)propane,1,1-bis(p-hydroxy-phenyl)cyclohexane, dihydroxybenzophenone,bifunctional polyether polyols based on ethylene oxide, propylene oxide,butylene oxide, or a mixture thereof, polytetra-hydrofuran,polycaprolactone, or polyesterols based on diols and dicarboxylic acids.

In another embodiment, hyperbranched polycarbonates comprised in themixtures of the invention can comprise not only the functional groupsalready obtained by means of the reaction (hydroxyl groups, carbonategroups or carbamoyl chloride groups) but also one or more furtherfunctional groups. The functionalization can be effected during themolecular-weight-increase process, or subsequently, i.e., after theactual poly-condensation is at an end.

If components which have not only hydroxyl or carbonate groups but alsofurther functional groups or functional elements are added before orduring the actual formation of the polycarbonates by polycondensation, ahyperbranched polycarbonate polymer having randomly distributedfunctionalities different from the carbonate, carbamoyl chloride orhydroxyl groups is obtained.

By way of example, these effects can be achieved by adding, duringpolycondensation, compounds bearing not only hydroxyl groups, carbonategroups or carbamoyl chloride groups but also further functional groupsor functional elements, such as mercapto groups, primary, secondary ortertiary amino groups, ether groups, carboxylic acid groups orderivatives thereof, sulfonic acid groups or derivatives thereof,phosphonic acid groups or derivatives thereof, silane groups, siloxanegroups, aryl radicals or long-chain alcohol radicals. Examples ofcompounds that can be used for modification by means of carbamate groupsare ethanolamine, propanolamine, isopropanolamine,2-(butylamino)ethanol, 2-(cyclohexylamino)ethanol, 2-amino-1-butanol,2-(2″-amino-ethoxy)ethanol, or higher alkoxylation products of ammonia,4-hydroxypiperidine, 1-hydroxyethylpiperazine, diethanolamine,dipropanolamine, diisopropanolamine, tris(hydroxymethyl)aminomethane,tris(hydroxyethyl)aminomethane, ethylenediamine, propylenediamine,hexamethylenediamine, or isophoronediamine.

An example of a compound that can be used for modification by mercaptogroups is mercaptoethanol. Tertiary amino groups can be produced by, forexample, incorporation of triethanolamine, tripropanolamine,N-methyldiethanolamine, N-methyl-dipropanolamine orN,N-dimethylethanolamine. Ether groups can, for example, be generated bycocondensation of bifunctional or higher-functional polyetherols.Addition of dicarboxylic acids, tricarboxylic acids, dicarboxylicesters, for example dimethyl terephthalate, or tricarboxylic esters canproduce ester groups. Reaction with long-chain alkanols or alkanediolscan introduce long-chain alkyl radicals. Reaction with alkyl or aryldiisocyanates generates polycarbonates which have alkyl, aryl andurethane groups, and addition of primary or secondary amines leads tointroduction of urethane or urea groups.

Subsequent functionalization can be obtained by reacting thehyperbranched poly-carbonate according to the invention in an additionalprocess step with a suitable functionalization reagent which can reactwith the OH and/or carbonate or carbamoyl chloride groups of thepolycarbonate.

Inventive hyperbranched polycarbonates comprising hydroxyl groups can,for example, be modified by addition of molecules comprising acid groupsor comprising isocyanate groups. By way of example, polycarbonatescomprising acid groups can be obtained by reaction with compoundscomprising anhydride groups. Furthermore, inventive hyper-branchedpolycarbonates comprising hydroxyl groups can also be converted tohigh-functionality polycarbonate polyether polyols by reaction withalkylene oxides, for example ethylene oxide, propylene oxide or butyleneoxide.

A preferred procedure in the preparation of hyperbranched polycarbonatescomprising stabilizing groups (b) mixes

-   -   (A) at least one compound having at least three alcoholic        hydroxyl groups per molecule    -   (B) with at least one reagent of the general formula I,    -   (C) with at least one reagent of the general formula        X³-(A¹)_(m)-X⁴    -   (D) and, if appropriate, with at least one compound having two        alcoholic hydroxyl groups per molecule        and heats the mixture to a temperature in the range from 60 to        260° C., preferably 80 to 220° C.

The reaction of compound (A) with reagent (B) and reagent (C) can becarried out in one step. However, it can also be carried out in twosteps, and, by way of example, compound (A) can firstly be reacted withreagent (B) to produce a hyperbranched polycarbonate and this can thenbe functionalized with reagent (C).

In the reaction with reagent (B), H—X¹ and H—X² are usually eliminated.When H—X¹ and/or H—X² are/is hydrogen halide, in particular HCl, thehydrogen halide(s) eliminated is/are preferably removed from thereaction mixture by addition of a base, for example in equimolar amountsbased on hydrogen halide to be eliminated. Suitable bases are, forexample, alkali metal hydroxides or organic amines, in particulartertiary amines, such as triethylamine and Hünig base(diisopropylethylamine). When H—X¹ and H—X² are alcohols, the alcohol(s)H—X¹ and H—X² eliminated is/are preferably removed by distillation,preferably during the reaction. The removal by distillation can becarried out at atmospheric pressure or under reduced pressure, forexample at 0.1 to 950 mbar, in particular at 100 to 900 mbar. Thedistillation is preferably carried out at atmospheric pressure.

The preparation process of the hyperbranched polycarbonates comprisingstabilizing groups (b) can be carried out in the presence of an organicsolvent which is preferably aprotic. Examples are decane, dodecane, orsolvent naphtha, also aromatic hydro-carbons, such as toluene,ethylbenzene, one or more isomeric xylenes, or chlorinated aromatichydrocarbons, such as chlorobenzene. Also suitable are ethers having asufficiently high boiling point, for example di-n-butyl ether or1,4-dioxane. Further suitable solvents are N,N-dimethylformamide andN,N-dimethylacetamide. However, the preparation of the hyperbranchedpolycarbonates comprising stabilizing groups (b) is preferably carriedout without use of solvents.

The preparation process of the hyperbranched polycarbonates comprisingstabilizing groups (b) can be carried out in the presence of a catalystor a catalyst mixture. Suitable catalysts are compounds which catalyzeesterification or transesterification reactions, for example alkalimetal hydroxides, alkali metal carbonates, alkali metalhydrogencarbonates, preferably of sodium, potassium or cesium, ororganic amines, in particular tertiary amines, guanidines, ammoniumcompounds, phosphonium compounds, organic compounds of aluminum, tin,zinc, titanium, zirconium or bismuth, and also double metal cyanide(DMC) catalysts as described, for example, in DE 10138216 or DE10147712.

Preference is given to use of potassium hydroxide, potassium carbonate,potassium hydrogencarbonate, sodium hydroxide, sodium carbonate, sodiumhydrogencarbonate, 1,4-diazabicyclo[2.2.2]octane (DABCO),diazabicyclononene (DBN), diazabicyclo-undecene (DBU), imidazoles, suchas imidazole, 1-methylimidazole or 1,2-dimethyl-imidazole, titaniumtetra-n-butylate, titanium tetraisopropylate, dibutyltin oxide,dibutyltin dilaurate, tin dioctoate, zirconium acetylacetonate, ormixtures thereof.

The amount added of the catalyst or catalyst mixture is generally from50 to 10 000 ppm by weight, preferably from 100 to 5000 ppm by weight,based on the amount of compound (A) used or the entirety of (A) and (D).

In general the hyperbranched polycarbonates comprising stabilizinggroups (b) are prepared in a pressure range from 0.1 mbar to 20 bar,preferably at 1 mbar to 5 bar.

The preparative process is for example carried out in reactors orreactor cascades which are operated batchwise, semicontinuously orcontinuously, for example in one or more tanks.

A hyperbranched polycarbonate can be prepared using:

from 10 to 59 mol % of compound (A), preferably from 10 to 55 mol %, andmore preferably up to 49 mol %, of compound (A),from 40 to 60 mol % of reagent (B), preferably from 45 to 55 mol %, andmore preferably about 50 mol %, of reagent (B),from 1 to 50 mol % of reagent (C), preferably up to 45 mol %, and morepreferably up to 40 mol %, of reagent (C),in each case based on the total reaction mixture of (A), (B), and (C).

The amount of the compound or compounds (D) used is normally from 0 to50 mol %, based on the compound (A), preferably from 0 to 45 mol %, morepreferably up to 40 mol %, and very preferably from 0 to 30 mol %.

By virtue of the abovementioned setting of the reaction conditions and,if appropriate, by virtue of the selection of the suitable solvent,hyperbranched polycarbonates comprising stabilizing groups (b) andobtained in the form of crude product can be further processed after thepreparation process, without further purification.

The hyperbranched polycarbonate according to the invention obtained ascrude product can additionally be stripped, i.e., freed of low molecularweight, volatile compounds. For this purpose, the catalyst canoptionally be deactivated after the desired conversion has been reachedand the low molecular weight volatile constituents, e.g., monoalcohols,phenols, carbonates, hydrogen chloride, or volatile oligomeric or cycliccompounds, can be removed by distillation, if appropriate withintroduction of a gas, preferably nitrogen, carbon dioxide or air, ifappropriate under reduced pressure.

There are various possible ways of stopping the intermolecularpolycondensation reaction of the preparative process of thehyperbranched polycarbonates comprising stabilizing groups (b). Forexample, the temperature can be reduced to a range in which the reactionceases and the hyperbranched polycarbonate is storage-stable. In anotherembodiment, the catalyst or catalyst mixture can be deactivated—in thecase of basic catalysts by, for example, addition of an acidiccomponent, a Lewis acid, for example, or an organic or inorganic proticacid.

The reaction can also be stopped automatically when the number ofterminal functional groups available for further reaction becomesinsufficient by virtue of reaction with reagent (C).

Moreover, as soon as a hyperbranched polycarbonate is present with thedesired degree of polycondensation, the reaction can be stopped byadding a product with groups reactive toward hyperbranched polycarbonatecomprising stabilizing groups (b). By way of example, a mono-, di- orpolyamine can be added or, for example, a mono-, di- or polyisocyanate,a compound comprising epoxy groups, or an acid derivative which isreactive with OH groups.

Particularly preferred as component (b) of the mixtures of the inventionare those hyperbranched carbonates, comprising stabilizing groups, inwhich as many as possible, and particularly all, of the substituents,symbols, and indices adopt their preferred or particularly preferreddefinition.

In a further preferred embodiment of the mixture of the invention thebranched polymer comprises urethane, allophanate, urea, biuret,uretdione, amide, isocyanurate, carbodiimide, uretonimine,oxadiazinetrione or iminooxadiazinedione groups and is referred to inthe context of the present invention as a branched polyisocyanate.Preferably there are urethane, allophanate, urea and/or biuret groupscomprised.

Di- and polyisocyanates comprise an average of from 2 to 10, preferablyfrom 2.1 to 10, more preferably from 2.2 to 8, isocyanate groups permolecule. Polyfunctional isocyanates are di- or polyisocyanates or theirmixtures.

Di- and polyisocyanates which are suitable are the prior-art aliphatic,cycloaliphatic, and aromatic isocyanates or mixtures thereof. Preferreddi- or polyisocyanates are diphenylmethane 4,4′-diisocyanate,diphenylmethane 2,4′-diisocyanate, the mixtures composed of monomericdiphenylmethane diisocyanates and of oligomeric diphenyl-methanediisocyanates (polymeric MDI), tolylene 2,4-diisocyanate, tolylene2,6-diisocyanate, naphthylene 1,5- and 2,6-diisocyanate, phenylene 1,3-and 1,4-diisocyanate, diphenyl diisocyanate, toluidine diisocyanate,triisocyanatotoluene, tetramethylene diisocyanate, hexamethylenediisocyanate, isophorone diisocyanate, methylenebis(cyclohexyl) 2,4′- or4,4′-diisocyanate, o-, m-, or p-xylylene diisocyanate,tetramethylxylylene diisocyanate, dodecyl diisocyanate, lysine alkylester diisocyanate, where alkyl is C₁ alkyl to C₁₀ alkyl, 2,2,4- or2,4,4-trimethylhexamethylene 1,6-diiso-cyanate,1,4-diisocyanatocyclohexane, 4-isocyanatomethyloctamethylene1,8-diiso-cyanate, 2-butyl-2-ethylpentamethylene diisocyanate,2-isocyanatopropylcyclohexyl isocyanate,3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,3- or1,4-bis-(isocyanatomethyl)cyclohexane, 1,4-diisocyanato-4-methylpentane,and 4-methyl-cyclohexane 1,3-diisocyanate (H-TDI).

It is preferable to use mixtures composed of two or more of theabove-mentioned polyisocyanates.

Suitable branched polyisocyanates are compounds which can be preparedfrom the abovementioned di- or polyisocyanates or their mixtures vialinking by means of urethane, allophanate, urea, biuret, uretdione,amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione, oriminooxadiazinedione structures. These linking mechanisms are describedfor example in Becker and Braun, Kunststoff-Handbuch Nr. 7 [PlasticsHandbook No. 7], Polyurethane [Polyurethanes], Carl-Hanser-Verlag Munich1993. It is preferable to use polyisocyanates which contain urethanestructures, allophanate structures, urea structures, biuret structures,isocyanurate structures, uretonimine structures, oxadiazinetrionestructures, or iminoxadiazinedione structures.

It is also possible to use mixtures of the abovementioned branchedpolyisocyanates as a basis for component (b) of the mixture of theinvention.

The linkage of the di- or polyisocyanates by way of urethane groupstakes place for example with use of alcohols or alcohol mixtures whosefunctionality is 2 or greater. By way of example, mention may be made ofthe reaction of 3 mol of hexamethylene diisocyanate, isophoronediisocyanate, tolylene diisocyanate, or diphenylmethylene diisocyanatewith ≦1 mol of triol, such as glycerol or trimethylolpropane, or elsethe reaction of two mol of an oligomeric diphenylmethane diisocyanate(polymeric MDI) with ≦1 mol of diol, such as ethylene glycol,butanediol, hexanediol, or with a polyoxy-alkylenediol. These reactionsform branched polyisocyanates whose functionality is greater than 2. Inthis connection see also Becker and Braun, Kunststoff-Handbuch Nr. 7[Plastics Handbook No. 7], Polyurethane [Polyurethanes],Carl-Hanser-Verlag Munich 1993, page 91.

Polyisocyanates comprising allophanate groups are produced frompolyisocyanates comprising urethane groups by reacting the urethanegroups with further isocyanate groups. In this connection, see alsoBecker and Braun, Kunststoff-Handbuch Nr. 7 [Plastics Handbook No. 7],Polyurethane [Polyurethanes], Carl-Hanser-Verlag Munich 1993, page 94.Another preparation route is the reaction of oxadiazinetriones withalcohols according to EP 825211. By way of example for the preparationof an allophanate, mention may be made of the reaction of hexamethylenediisocyanate or isophorone diisocyanate with monoalcohols, whichaccording to GB 994 890, EP 496 208, EP 524 500, or EP 524 501 giveoligoisocyanates whose functionality is greater than 2. Mention may alsobe made of the reaction of hexamethylene diisocyanate or isophoronediisocyanate with di- or polyhydric alcohols, as described by way ofexample in EP 1122273. These reactions form branched polyisocyanateshaving functionality greater than 2.

By way of example, polyisocyanates comprising urea groups and comprisingbiuret groups may be prepared via reactions of isocyanates with water orwith amines. In this connection see also Becker and Braun,Kunststoff-Handbuch Nr. 7 [Plastics Handbook No. 7], Polyurethane[Polyurethanes], Carl-Hanser-Verlag Munich 1993, page 95. By way ofexample, mention may be made of the reaction of hexamethylenediisocyanate or isophorone diisocyanate with water or withwater-generating substances, as are described in DE-A 28 08 801, DE-A 3403 277, or DE-A 15 43 178. These reactions form branched polyisocyanateshaving functionality greater than 2.

Polyisocyanates comprising isocyanurate structures are obtained bycatalytic or thermal cyclization of three isocyanate groups. If di- orpolyisocyanates are used as starting compounds, the products aregenerally not only the actual trimers but also higher oligomericpolyisocyanates. The overall functionality of these polyisocyanates istherefore greater than 3. In this connection see also Becker and Braun,Kunststoff-Handbuch Nr. 7 [Plastics Handbook No. 7], Polyurethane[Polyurethanes], Carl-Hanser-Verlag Munich 1993, page 91. By way ofexample, mention may be made of the preparation of branchedpolyisocyanates via isocyanuratization of hexamethylene diisocyanate orof isophorone diisocyanate, a possible method for which is thataccording to DE-A 29 16 201 or DE-A 38 10 908.

Polyisocyanates comprising uretonimine groups are obtained via furtherreaction of isocyanate groups with polyisocyanates comprisingcarbodiimide groups. In this connection see also Becker and Braun,Kunststoff-Handbuch Nr. 7 [Plastics Handbook No. 7], Polyurethane[Polyurethanes], Carl-Hanser-Verlag Munich 1993, page 94.

Polyisocyanates comprising oxadiazinetrione groups are obtained viareaction of di- or polyisocyanates with carbon dioxide, as described forexample in DE-A 16 70 666.

Polyisocyanates comprising iminooxadiazinedione groups can be regardedas asymmetric relatives of the polyisocyanates comprising isocyanurategroups. The preparation of these compounds is described for example inDE-A 197 34 048.

Preferably use is made of aliphatic or cycloaliphatic branched di- orpolyisocyanates which comprise isocyanurate, urethane, allophanate, ureaor biuret groups.

The branched polyisocyanates comprised in the mixtures of the inventioncomprise one or more stabilizing groups, with stabilized additivescorresponding to the stabilizing groups being coupled to thepolyisocyanates via functional groups which are able to react chemicallywith the NCO groups of the polyisocyanates and in so doing to form acovalent bond.

One class of stabilizing groups which act as antioxidants are stericallyhindered phenol groups. Corresponding sterically hindered phenol groupshave already been described above for the case of the hyperbranchedpolycarbonates and are also used for the case of the branchedpolyisocyanates. The sterically hindered phenol groups preferred in thecase of the hyperbranched polycarbonates are also preferred in the caseof the branched polyisocyanates.

A further group of stabilizing groups which function as lightstabilizers are based on HALS compounds. Corresponding HALS groups orHALS compounds have already been described above for the case of thehyperbranched polycarbonates and are also used for the case of thebranched polyisocyanates. The HALS groups or HALS compounds preferred inthe case of the hyperbranched polycarbonates are also preferred in thecase of the branched polyisocyanates.

A further group of stabilizing groups are aromatic amine groups.Corresponding aromatic amine groups have already been described abovefor the case of the hyperbranched polycarbonates and are also used forthe case of the branched polyisocyanates. The aromatic amine groupspreferred in the case of the hyperbranched polycarbonates are alsopreferred in the case of the branched polyisocyanates.

In a further embodiment of the mixture of the invention the branchedpolyisocyanates comprise two different stabilizing groups, one of thesegroups being based on sterically hindered phenols and the other beingbased on HALS compounds.

The branched polyisocyanates comprising stabilizing groups are typicallyprepared by way of a polyaddition reaction such that at least onebranched polyisocyanate as anchor group is introduced as an initialcharge in a reaction vessel, if appropriate with the further use of anorganic solvent, under an inert gas atmosphere, preferably undernitrogen, and this initial charge is brought to reaction temperaturewith stirring. Subsequently, at reaction temperature, at least onestabilizing group is added continuously or discontinuously. The amountof stabilizing group is dependent on the number of NCO groups of thebranched polyisocyanate and is preferably selected such that the ratioof the molar number of isocyanate groups to the molar number of groupsof the active substance that are reactive therewith is substantially1:1. Where two or more active substances are reacted simultaneously orsuccessively with the poly-isocyanate, the total amount of the reactivegroups of the active substances is made such that it correspondssubstantially to the total amount of the isocyanate groups. The branchedpolyisocyanates thus prepared, comprising stabilizing groups, may,however, also have up to 20 mol %, preferably up to 10 mol %, of freeNCO groups, i.e., NCO groups which have not been consumed by reactionwith the stabilizing group. Preferably, however, the stabilizers of theinvention have substantially no free NCO groups.

The reaction time is generally selected such that the NCO groups of thebranched polyisocyanates are reacted completely with the reactive groupsof the stabilizing group. The aforementioned reaction with thestabilizing groups and the auxiliaries may take place, if appropriate,in the presence of catalysts, which are used in amounts of 0.0001% to 1%by weight, more particularly of 0.001% to 0.1% by weight, based in eachcase on the amount of the branched polyisocyanates. Suitable catalystsfor polyaddition reactions include organometallic compounds, especiallyorganotin, organozinc, organotitanium, organobismuth or organozirconiumcompounds. Particular preference is given to using, for example,dibutyltin dilaurate, dibutyltin oxide, titanium tetrabutylate, zincacetylacetonate or zirconium acetylacetonate. Additionally it ispossible to use strong bases, preferably nitrogen compounds, such astributylamine, quinuclidine, diazabicyclooctane, diazabicyclononane,diazabicyclononene, diaza-bicycloundecane or diazabicycloundecene.

Suitable solvents which can be used are those which are inert toward thereactants under reaction conditions. Suitability is possessed forexample by acetone, 2-butanone, ethyl acetate, butyl acetate,tetrahydrofuran, dioxane, benzene, toluene, xylene, ethyl-benzene,chlorobenzene, dichlorobenzene, dimethylformamide, dimethylacetamide orN-methylpyrrolidone.

The reaction temperature for the polyaddition reaction is typically −10to 220° C., preferably 0 to 180° C. The reaction takes place both atatmospheric pressure and at a pressure above or else below atmosphericpressure, such as, for example, at a pressure of 2 to 20 bar or at 0.1to 0.001 bar.

In one embodiment of the present invention, mixtures of the inventioncomprise branched polyisocyanates with stabilizing groups, of which acharacteristic feature is that these polyisocyanates have a dynamicviscosity in the range from 100 to 150 000 mPa·s, preferably up to 10000 mPa·s, determined at 40° C., in analogy for example to DIN 53019.

In one embodiment of the present invention, mixtures of the inventioncomprise branched polyisocyanates with stabilizing groups, acharacteristic feature of which is that these polyisocyanates have anumber-average molecular weight (M_(e)) of 100 to 15 000, preferably of200 to 12 000, and more particularly of 400 to 10 000 g/mol, which canbe determined, for example, by GPC, polymethyl methacrylate (PMMA) asstandard and tetrahydrofuran as eluent.

In one preferred embodiment of the present invention, mixtures of theinvention comprise branched polyisocyanates having stabilizing groups, acharacteristic feature of which is that these polyisocyanates have adynamic viscosity in the range from 100 to 150 000 mPa·s, preferably upto 10 000 mPa·s, determined at 40° C., in analogy for example to DIN53019, and that these polyisocyanates have a number-average molecularweight (M_(n)) of 100 to 15 000, preferably of 200 to 12 000, and moreparticularly of 400 to 10 000 g/mol, which can be determined, forexample, by GPC, polymethyl methacrylate (PMMA) as standard andtetrahydrofuran as eluent.

In one embodiment of the mixture of the invention the polymer used asbranched polymer comprising stabilizing groups is the polymer obtainedby the reaction of a mixture comprising:

-   -   (A′) one or more polyfunctional isocyanates,    -   (B′) one or more HALS compounds comprising a functional group        reacting with (A′),    -   (C′) inert solvent or mixtures of inert solvents,    -   (D′) optionally catalyst.

In this system the isocyanate (A′) preferably has a functionality ofmore than 2 and more preferably the isocyanate (A′) is an oligomericisocyanate based on hexa-methylene diisocyanate or isophoronediisocyanate.

Preferably, furthermore, the HALS compound (B′) is a compound of theabove-described general formula (III) where R²¹ reacts with thepolyfunctional isocyanate (A′) or with the NCO groups of the branchedpolyisocyanate.

With very particular preference R²¹═OH, R²²═R²³═R²⁴═R²⁵═R²⁶=methyl, andR²⁷═R²⁸═H.

The inert solvent (C′) is preferably acetone, 2-butanone,tetrahydrofuran, ethyl acetate or butyl acetate.

The optional catalyst (D′) is preferably dibutyltin dilaurate,dibutyltin oxide or titanium tetrabutylate.

In the mixtures of the invention component (c) may further compriseoptionally one or more additions.

Optional further additions (c)

Optionally the mixture of the invention comprises as component (c), orthe inanimate organic material to be stabilized by the mixturecomprises, in addition, at least one further light stabilizer and/orfurther (co)stabilizers. Suitable light stabilizers and further(co)stabilizers are selected, for example, from groups a) to s):

-   a) 4,4-diarylbutadienes,-   b) cinnamic esters,-   c) benzotriazoles,-   d) hydroxybenzophenones,-   e) diphenylcyanoacrylates,-   f) oxamides,-   g) 2-phenyl-1,3,5-triazines,-   h) antioxidants,-   i) nickel compounds,-   j) sterically hindered amines not attached as stabilizing groups to    branched polymer,-   k) metal deactivators,-   l) phosphites and phosphonites,-   m) hydroxylamines,-   n) nitrones,-   o) amine oxides,-   p) benzofuranones and indolinones,-   q) thiosynergists,-   r) peroxide-destroying compounds, and-   s) basic costabilizers.

Group a) of the 4,4-diarylbutadienes includes for example compounds ofthe formula (aa)

The compounds are known from EP-A-916 335. The substituents R¹⁹ and R²⁰,independently of one another, identically or differently, are preferablyC₁-C₈ alkyl and C₅-C₈ cycloalkyl.

Group b) of the cinnamic esters includes for example 2-isoamyl4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methylα-methoxycarbonylcinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate,butyl α-cyano-β-methyl-p-methoxycinnamate, and methylα-methoxycarbonyl-p-methoxycinnamate.

Group c) of the benzotriazoles includes for example2-(2′-hydroxyphenyl)benzo-triazoles such as2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)-benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzo-triazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];the product of esterifying2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH2CH2—COO(CH2)3]2 whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl and mixturesthereof.

Group d) of the hydroxybenzophenones includes for example2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone,2,2′-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone,2,2′,4,4′-tetrahydroxybenzo-phenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxy-benzophenone,2-hydroxy-4-(2-ethylhexyloxy)benzophenone,2-hydroxy-4-(n-octyloxy)-benzophenone,2-hydroxy-4-methoxy-4′-methylbenzophenone,2-hydroxy-3-carboxy-benzophenone,2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, and2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5,5′-bissulfonic acid and itssodium salt.

Group e) of the diphenylcyanoacrylates includes for example ethyl2-cyano-3,3-diphenylacrylate, obtainable commercially for example underthe name Uvinul® 3035 from BASF AG, Ludwigshafen, 2-ethylhexyl2-cyano-3,3-diphenylacrylate, obtainable commercially for example asUvinul® 3039 from BASF AG, Ludwigshafen, and1,3-bis[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis{[Z-cyano-3′,3′-diphenyl-acryloyl)oxy]methyl}propane,obtainable commercially for example under the name Uvinul® 3030 fromBASF AG, Ludwigshafen.

Group f) of the oxamides includes for example 4,4′-dioctyloxyoxanilide,2,2′-di-ethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, and also mixtures ofortho-, para-methoxy-disubstituted oxanilides and mixtures of ortho- andpara-ethoxy-disubstituted oxanilides.

Group g) of the 2-phenyl-1,3,5-triazines includes for example2-(2-hydroxyphenyl)-1,3,5-triazines such as2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxy-phenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/-tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

Group h) of the antioxidants comprises, for example: Alkylatedmonophenols such as, for example, 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butyl-phenol, 2,6-di-tert-butyl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-(a-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, unbranched orsidechain-branched nonylphenols such as, for example,2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundec-1-yl)phenol,2,4-dimethyl-6-(1-methylheptadec-1-yl)-phenol,2,4-dimethyl-6-(1-methyltridec-1-yl)phenol, and mixtures thereof.

Alkylthiomethylphenols such as, for example,2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol and2,6-didodecylthiomethyl-4-nonylphenol.

Hydroquinones and alkylated hydroquinones such as, for example,2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, and bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

Tocopherols, such as, for example, α-tocopherol, β-tocopherol,γ-tocopherol, δ-tocopherol, and mixtures thereof (vitamin E).

Hydroxylated thiodiphenyl ethers such as, for example,2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol), and4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

Alkylidenebisphenols such as, for example,2,2′-methylenebis(6-tert-butyl-4-methyl-phenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutyl-phenol),2,2′-methylenebis[6-(a-methylbenzyl)-4-nonylphenol],2,2′-methylenebis-[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclo-pentadiene,bis[2-(3′-tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyl-mercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

Benzyl compounds such as, for example,3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxy-dibenzyl ether, octadecyl4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)-amine,1,3,5-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,di(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl3,5-di-tert-butyl-4-hydroxybenzylmercapto-acetate,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester, and3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium salt.

Hydroxybenzylated malonates such as, for example, dioctadecyl2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, andbis[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-malonate.

Hydroxybenzyl aromatics such as, for example,1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

Triazine compounds such as, for example,2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-phenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

Benzylphosphonates such as, for example, dimethyl2,5-di-tert-butyl-4-hydroxy-benzylphosphonate, diethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate (diethyl(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methylphosphonate),dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl5-tert-butyl-4-hydroxy-3-methyl-benzylphosphonate, and the calcium saltof monoethyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate.

Acylaminophenols such as, for example, 4-hydroxylauranilide,4-hydroxystearanilide,2,4-bisoctylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine, andoctyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmonohydric or polyhydric alcohols, such as with methanol, ethanol,n-octanol, isooctanol, octa-decanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxalamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid withmonohydric or polyhydric alcohols, such as with methanol, ethanol,n-octanol, isooctanol, octa-decanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxalamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmonohydric or polyhydric alcohols, such as with methanol, ethanol,octanol, octadecanol, 1,6-hexane-diol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and4-hydroxymethyl-1-phospha-2,6,7-trioxa-bicyclo[2.2.2]octane.

Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydricor polyhydric alcohols, such as with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and4-hydroxymethyl-1-phospha-2,6,7-trioxa-bicyclo[2.2.2]octane.

Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such asN,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxy-phenyl]propionyloxy)ethyl]oxamide(e.g., Naugard®XL-1 from Uniroyal).

Ascorbic Acid (vitamin C)

Amine antioxidants, such as, for example,N,N′-diisopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylene-diamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methyl-heptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxy-diphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for example,p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoyl-aminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxy-phenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenyl-methane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenyl-methane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,o-tolyl biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthyl-amine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyl-diphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol,the dimethyl succinate polymer with4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol [CAS number65447-77-0], (for example, Tinuvin® 622 from Ciba Specialty Chemicals,Inc.), polymer of2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-oneand epichlorohydrin [CAS No.: 202483-55-4], for example (Hostavin® N 30from Clairant).

Group i) of the nickel compounds includes for example nickel complexesof 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters suchas of the methyl or ethyl esters, for example, nickel complexes ofketoximes such as, for example, of 2-hydroxy-4-methyl-phenyl undecylketoxime, and the nickel complex of1-phenyl-4-lauroyl-5-hydroxy-pyrazole, with or without additionalligands.

Group j) of the sterically hindered amines includes for example4-hydroxy-2,2,6,6-tetra-methylpiperidine,1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl) succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-penta-methyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate(n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acidbis(1,2,2,6,6-pentamethylpiperidyl) ester), condensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensation products ofN,N′-bis(2,2,6,6-tetra-methyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetra-methyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)bis-(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyl-oxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-tri-azaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cycliccondensation products ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, condensation product of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine andalso 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecyl-succinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane,reaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxy-phenyl)ethene,diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxo-4-(2,2,6,6-tetramethyl-4-piperidyl)]-siloxane,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine, the reaction product of1-oxyl-4-hydroxy-2,2,6,6-tetra-methylpiperidine and a carbon radical oft-amyl alcohol,1-(2-hydroxy-2-methyl-propoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl)sebacate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl)adipate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidin-4-yl)succinate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidin-4-yl)glutarate,2,4-bis{N[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine,hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidyl)-1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaazacyclopenta-[def]fluorene-4,8-dione(e.g. Uvinul® 4049 from BASF AG, Ludwigshafen),poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]])[CAS No. 71878-19-8], 1,3,5-triazine-2,4,6-triamine,N,N′″-[1,2-ethanediylbis-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]bis[N′,N″-dibutyl-N′,N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)(CAS No. 106990-43-6) (e.g., Chimassorb 119 from Ciba SpecialtyChemicals, Inc.).

Group k) of the metal deactivators includes for exampleN,N′-diphenyloxalamide, N-salicylal-N′-salicyloylhydrazine,N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl-bisphenyl hydrazide,N,N′-diacetyladipic dihydrazide, N,N′-bis(salicyloyl)oxalic dihydrazide,and N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

Group l) of the phosphites and phosphonites includes for exampletriphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkylphosphites, tris(nonylphenyl) phosphite, trilauryl phosphite,trioctadecyl phosphite, distearyl pentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methyl-phenyl) pentaerythritol diphosphite,diisodecyloxy pentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepine,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g][1,3,2]dioxaphosphocine,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], and2-ethylhexyl-(3,3′,5,5′-tetra-tert-butyl-1,1-biphenyl-2,2′-diyl)phosphite.

Group m) of the hydroxylamines includes for exampleN,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine,N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine,N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecyl-hydroxylamine, N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecyl-hydroxylamine,N-methyl-N-octadecylhydroxylamine, and N,N-dialkylhydroxylamine fromhydrogenated tallow fatty amines.

Group n) of the nitrones includes for example N-benzyl α-phenyl nitrone,N-ethyl α-methyl nitrone, N-octyl α-heptyl nitrone, N-lauryl α-undecylnitrone, N-tetradecyl α-tridecyl nitrone, N-hexadecyl α-pentadecylnitrone, N-octadecyl α-heptadecyl nitrone, N-hexadecyl α-heptadecylnitrone, N-octadecyl α-pentadecyl nitrone, N-heptadecyl α-heptadecylnitrone, N-octadecyl α-hexadecyl nitrone, N-methyl α-heptadecyl nitrone,and nitrones derived from N,N-dialkylhydroxylamines prepared fromhydrogenated talc fatty amines.

Group o) of the amine oxides includes for example amine oxidederivatives as described in U.S. Pat. Nos. 5,844,029 and 5,880,191,didecylmethylamine oxide, tridecylamine oxide, tridodecylamine oxide,and trihexadecylamine oxide.

Group p) of the benzofuranones and indolinones includes for examplethose described in U.S. Pat. Nos. 4,325,863; 4,338,244; 5,175,312;5,216,052; 5,252,643; in DE-A-4316611; in DE-A-4316622; in DE-A-4316876;in EP-A-0589839 or EP-A-0591102, or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxy-phenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzo-furan-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, IrganoxsHP-136 from Ciba Specialty Chemicals, and3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

Group q) of the thiosynergists includes for example dilaurylthiodipropionate or distearyl thiodipropionate.

Group r) of the peroxide-destroying compounds includes for exampleesters of β-thiodipropionic acid, for example, the lauryl, stearyl,myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyldithio-carbamate, dioctadecyldisulfide, and pentaerythritol tetrakis(β-dodecylmercapto)-propionate.

Group s) of the basic costabilizers includes for example melamine,polyvinyl-pyrrolidone, dicyandiamide, triallylcyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal and alkaline earth metal salts of higher fatty acids, forexample, calcium stearate, zinc stearate, magnesium behenate, magnesiumstearate, sodium ricinoleate, and potassium palmitate, antimonypyrocatecholate or zinc pyrocatecholate.

The mixture of the invention, as component (c), or the plastic mayfurther comprise other additives and additions t). Suitable additivesfrom the group t) are the customary additives, such as pigments, dyes,nucleating agents, fillers, reinforcing agents, antifogging agents,biocides, and antistats, for example.

Suitable pigments are inorganic pigments, examples being titaniumdioxide in its three modifications—rutile, anatase or brookite;ultramarine blue, iron oxides, bismuth vanadates or carbon black, andalso the class of the organic pigments, examples being compounds fromthe class of the phthalocyanines, perylenes, azo compounds,isoindolines, quinophthalones, diketopyrrolopyrroles, quinacridones,dioxazines, and indanthrones.

By dyes are meant all colorants which dissolve completely in the plasticused or are present in a molecularly disperse distribution and cantherefore be used for the high-transparency, nonscattering coloring ofpolymers. Likewise regarded as dyes are organic compounds which exhibita fluorescence in the visible part of the electromagnetic spectrum, suchas fluorescent dyes.

Suitable nucleating agents include for example inorganic substances,examples being talc, metal oxides such as titanium dioxide or magnesiumoxide, phosphates, carbonates or sulfates, preferably of alkaline earthmetals; organic compounds such as monocarboxylic or polycarboxylic acidsand also their salts, such as 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate or sodium benzoate; and polymericcompounds, such as ionic copolymers (“ionomers”), for example.

Suitable fillers and reinforcing agents include for example calciumcarbonate, silicates, talc, mica, kaolin, barium sulfate, metal oxidesand metal hydroxides, carbon black, graphite, wood flour and flours orfibers of other natural products, and synthetic fibers. Further suitableexamples of fibrous or pulverulent fillers include carbon or glassfibers in the form of glass fabrics, glass mats or filament glassrovings, chopped glass, glass beads, and wollastonite. Glass fibers canbe incorporated either in the form of short glass fibers or in the formof continuous fibers (rovings).

Examples of suitable antistats include amine derivatives such asN,N-bis(hydroxy-alkyl)alkylamines or -alkylenamines, polyethylene glycolesters and ethers, ethoxylated carboxylic esters and carboxamides, andglyceryl mono- and distearates, and also mixtures thereof.

With preference there are antioxidants, flame retardants and/orcolorants comprised as optional component (c) in the mixtures of theinvention.

The weight ratio of components (a) and (b) in the mixtures of theinvention is generally from 5:1 to 1:5, preferably from 2:1 to 1:2, morepreferably from 1.2:1 to 1:1.2, with more particular preference beinggiven to a mixture in the weight ratio of approximately 1:1.

If component (c) is present, the weight ratio of the sum of components(a) and (b) to component (c) in the mixtures of the invention isgenerally from 100:1 to 2:1, preferably from 50:1 to 5:1, morepreferably from 30:1 to 7:1, more particular preference being given to amixture in the weight ratio of approximately 10:1.

The mixtures of the invention can be prepared by known processesfamiliar to the skilled worker.

For example, if component (b) is a solid, component (b) can be added tothe liquid component (a) with mixing.

If component (b) is itself liquid, then processes known to the skilledworker for the mixing of liquids can be used for mixing it with theliquid component (a).

In one preferred embodiment the mixture of the invention is liquid.

Generally speaking the components (a), (b), and, optionally, (c) can bemixed in any order.

For example, component (c) can be added to the mixture of components (a)and (b), and the resulting mixture can then be homogenized.

Alternatively components (c) may be admixed to (a) and/or (b) first, andthen the end mixture produced.

The invention also provides, accordingly, a corresponding process forpreparing the mixtures of the invention.

The mixtures of the invention may also only be produced in the inanimateorganic materials to be stabilized, by the addition of components (a),(b), and, optionally, (c).

It may be advantageous to carry out the mixing of the components at anelevated temperature. More particularly component (a) and optionallycomponent (c) may be added immediately after the synthesis of component(b).

Particular preference is given to the following combinations ofcompounds of components (a) and the branched polymers comprisingstabilizing groups (b) of the formulae IIa and IIb:

-   1. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds of the    formulae IIa or IIb based on 4-amino-2,2,6,6-tetramethylpiperidine,-   2. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds of the    formulae IIa or IIb based on    4-amino-1,2,2,6,6-pentamethylpiperidine,-   3. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds of the    formulae IIa or IIb based on    4-hydroxy-2,2,6,6-tetramethylpiperidine,-   4. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds of the    formulae IIa or IIb based on    4-hydroxy-1,2,2,6,6-pentamethylpiperidine,-   5. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds of the    formulae IIa or IIb based on    4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl,-   6. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds of the    formulae IIa or IIb based on    4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl,-   7. 2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae IIa    or IIb based on 4-amino-2,2,6,6-tetramethylpiperidine,-   8. 2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae IIa    or IIb based on 4-amino-1,2,2,6,6-pentamethylpiperidine,-   9. 2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae IIa    or IIb based on 4-hydroxy-2,2,6,6-tetramethylpiperidine,-   10. 2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae    IIa or IIb based on 4-hydroxy-1,2,2,6,6-pentamethylpiperidine,-   11. 2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae    IIa or IIb based on 4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl,-   12. 2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae    IIa or IIb based on 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl,

The mixtures of the invention are outstandingly suitable for use asstabilizers for stabilizing inanimate organic material against theeffect of light, oxygen, and heat. The mixtures of the invention aregenerally added to the inanimate organic materials to be stabilized at aconcentration sufficient to achieve the desired stabilization effect(i.e., the effective amount). The mixtures of the invention are addedpreferably in a concentration of 0.01% to 5% by weight, more preferablyof 0.02% to 1% by weight, based on the inanimate organic material,before, during or after the production of the inanimate organicmaterial.

The invention further provides a method of stabilizing inanimate organicmaterials, more particularly plastics and coating materials, against theeffect of light, oxygen, and heat, which comprises adding the mixturesof the invention to the inanimate organic materials, preferably in theconcentrations indicated above.

The mixture of the invention may be added to the inanimate organicmaterial to be protected in the form of a prefabricated mixture ofcomponents (a), (b), and, optionally, (c), although it is likewisepossible to add components (a), (b), and, optionally, (c) separately tothe material to be protected, in which case the mixture is formed onlyin the material to be protected. In the case where components (a), (b),and, optionally, (c) are added separately they may be addedsimultaneously or at different times, the sequence of addition generallybeing immaterial.

By inanimate organic material is meant, for example, cosmetic productssuch as ointments and lotions, drug formulations such as pills andsuppositories, photographic recording material such as photographicemulsions, or intermediates for plastics and coating materials, but moreparticularly plastic and coating materials themselves. From inanimateorganic material it is possible to produce articles.

The invention further provides inanimate organic material, moreparticularly plastics and coating materials, which are stabilizedagainst the effect of light, oxygen, and heat and which comprise themixtures of the invention, preferably in the concentrations indicatedabove.

For the mixing of the mixture of the invention primarily with plasticsit is possible to employ all known apparatus and methods of mixingstabilizers or other adjuvants into polymers.

Examples of plastics which can be stabilized by means of the mixtures ofthe invention include the following:

thermoplastic elastomers;polymers of mono- and diolefins, such as, for example, low-density andhigh-density polyethylene, polypropylene, linear polybut-1-ene,polyisoprene, polybutadiene, and copolymers of mono- or diolefins, ormixtures of said polymers;copolymers of mono- or diolefins with other vinyl monomers, such as, forexample, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylatecopolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acidcopolymers;polystyrene and also copolymers of styrene or α-methylstyrene withdienes and/or acrylic derivatives, such as, for example,styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethylmethacrylate, styrene-butadiene-ethyl acrylate,styrene-acrylonitrile-methacrylate, acrylonitrile-butadiene-styrene(ABS) or methyl methacrylate-butadiene-styrene (MBS):halogenated polymers, such as polyvinyl chloride, polyvinyl fluoride,polyvinylidene fluoride, and their copolymers, for example;polymers deriving from α,β-unsaturated acids and their derivatives, suchas polyacrylates, polymethacrylates, polyacrylamides, andpolyacrylonitriles;polymers deriving from unsaturated alcohols and amines and/or theiracrylic derivatives or acetals, such as polyvinyl alcohol and polyvinylacetate, for example;polyurethanes, polyamides, polyureas, polyesters, polycarbonates,polysulfones, polyethersulfones, and polyetherketones.

Additionally it is possible to use the mixtures of the invention tostabilize coatings, industrial coatings for example. Particular emphasisamong these may be given to baking varnish systems, more particularlyvehicle finishes, preferably two-coat finishes. Another field of use isthat, for example, of coating materials for the exterior coating ofbuildings, other constructions or technical apparatus.

The mixtures of the invention may be added in solid or dissolved form tothe coating material. In this context their high solubility in coatingsystems is a particular advantage.

The mixtures of the invention are preferably used to stabilizethermoplastic elastomers, based for example on polyolefins. The mixturesof the invention find use more particularly in the stabilization ofmolding compounds comprising the stated materials.

Another preferred field of use is the stabilization of low-density andhigh-density polyethylene, and also of polypropylene and polyamide,including, for example, fibers of said polymers.

Likewise preferred is the use of the mixtures of the invention forstabilizing plastics composed of at least one polymer selected fromthermoplastic elastomers, polyolefins, polystyrene, copolymers ofstyrene or of α-methylstyrene, polyesters and polyethers,polycarbonates, polyvinyl chloride, polyacrylates, polymethacrylates,polyurethanes, and physical blends of the aforementioned polymers.

The mixtures of the invention exhibit improved stabilization ofinanimate organic materials with respect to light with a high UVfraction and/or high light intensity. Furthermore, the mixtures of theinvention are based on easily accessible starting materials. By means ofthe mixtures of the invention it is possible to ensure efficientprotection of inanimate organic materials with respect to oxygen orheat.

The above embodiments of the process of the invention, and the examplesbelow, exemplarily illustrate the present invention. However, for aperson skilled in the art, there are many further variations of theprocess, and combinations of the features of the process of theinvention, that are conceivable without departing the scope of theclaims.

EXAMPLES Example 1 Preparation of Mixtures of the Invention

972 g of trimethylolpropane, randomly etherified with 1 mol of ethyleneoxide per mole of hydroxyl groups, 411 g of1,2,2,6,6-pentamethylpiperidin-4-ol, and 709 g of diethyl carbonate werecharged to a reaction vessel equipped with stirrer, reflux condenser,and internal thermometer, and then 0.2 g of potassium carbonate wasadded and the mixture was heated to 140° C. with stirring and stirred at140° C. for 3.5 h. Thereafter the reflux condenser was swapped for adescending condenser, ethanol was removed by distillation, and thetemperature of the reaction mixture was slowly raised to 200° C. Thedistillate (490 g) was collected in a cooled, round-bottomed flask. Thenthe reaction mixture was cooled to 140° C., 0.1 g of 85% strengthphosphoric acid was added for deactivation, and the mixture was thenfreed from volatiles at 100 mbar for 10 min. Subsequently the productwas cooled to room temperature and analyzed by gel permeationchromatography; the eluent was dimethylacetamide and the calibrationstandard used was polymethyl methacrylate (PMMA). The number-averagemolecular weight, Mn, was 810 g/mol and the weight-average molecularweight, Mw, was 1590 g/mol. The viscosity, determined at 23° C. inaccordance with DIN 53019, was 1100 mPas.

500 g of the polycarbonate of the invention comprising stabilizer groupswere then heated to 80° C., 500 g of 2-ethylhexyl2-cyano-3,3-diphenylacrylate (CAS No. 6197-30-4) were added, and themixture was stirred to homogeneity for 2 h. The viscosity of thestabilizer mixture, determined at 23° C. in accordance with DIN 53019,was 5800 mPas.

Example 2 Preparation of Mixtures of the Invention

A reaction vessel with stirrer, gas inlet tube, and dropping funnel withpressure compensation was charged, under dry nitrogen blanketing, with588 g of BASONAT® HA 300, in solution in an equal amount by weight ofdry 2-butanone, 300 ppm (based on isocyanate) of dibutyltin dilauratewere added at room temperature, and the mixture was heated to 50° C.Then 453.6 g of 1,2,2,6,6-pentamethylpiperidin-4-ol, in solution in thesame amount by weight of dry 2-butanone, were added dropwise over thecourse of 30 min. After the end of the addition the reaction mixture wasstirred at 50° C. for 1 h more. Subsequently the solvent was removedunder reduced pressure on a rotary evaporator. The average molar massesof the polymeric stabilizer were determined by means of gel permeationchromatography (GPC). Elution was carried out with tetrahydrofuran asthe mobile phase, and the columns were calibrated with polymethylmethacrylate as standard. Mn=1060 g/mol, Mw=1190 g/mol.

500 g of the polyurethane of the invention comprising stabilizer groupswere then heated to 80° C. in a round-bottomed flask, 500 g of2-ethylhexyl 2-cyano-3,3-diphenylacrylate (CAS No. 6197-30-4) wereadded, and the mixture was stirred to homogeneity for 2 h. The viscosityof the stabilizer mixture, determined at 40° C. in accordance with DIN53019, was 8100 mPas.

BASONAT® HA 300 (BASF AG): allophanate-group-comprising polyisocyanatebased on hexamethylene diisocyanate; the viscosity at 23° C. (DIN 53019)is 200-400 mPas.

1. A mixture comprising (a) one or more UV absorbers which are liquid ata temperature of from 5 to 40° C. and a pressure of from 500 to 1500mbar, with the proviso that the mixture of 95% benzene propanoic acid3-2(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-C₇₋₉-branchedand linear alkyl esters and 5% 1-methoxy-2-propyl acetate as a liquid UVabsorber is excluded, (b) one or more branched polymers comprising astabilizing group, (c) optionally one or more further additions.
 2. Themixture according to claim 1, wherein the branched polymers comprising astabilizing group (b) are liquid at room temperature.
 3. The mixtureaccording to claim 1, wherein the mixture is liquid at room temperature.4. The mixture according to claim 1, wherein the UV absorber (a) isselected from the group consisting of cyanoacrylate, cinnamic estersester, benzotriazole, and triazine.
 5. The mixture according to claim 4,wherein the UV absorber (a) is 2-ethylhexyl 2-cyano-3,3-diphenylacrylateor 2-ethylhexyl 4-methoxycinnamate.
 6. The mixture according to claim 1,wherein the one or more branched polymers comprising a stabilizing groupcomprise a hyperbranched structure.
 7. The mixture according to claim 1,wherein the branched polymer comprises a carbonate group.
 8. The mixtureaccording to claim 1, wherein the branched polymer comprises urethane,allophanate, urea and/or biuret groups.
 9. The mixture according toclaim 1, wherein the branched polymer comprises a HALS group as astabilizing group.
 10. The mixture according to claim 1, furthercomprising as optional component (c) an antioxidant, a flame retardantand/or a colorant. 11-13. (canceled)
 14. A plastic comprising at leastone mixture according to claim
 1. 15. An article produced from plasticsaccording to claim
 14. 16. A method of stabilizing plastic against theeffect of light, oxygen and/or heat, which comprises adding to saidplastic at least one mixture according to claim 1, in an effectiveamount.